Phosphorus Containing Rubber Seed oil as a Flame Retardant Plasticizer for Polyvinyl Chloride

The application of phthalate plasticizers has been restricted around the world due to their poor migration and potential harm to the human body.Hence,producing functional bio-based plasticizers via exploiting clean and reusable resources meets the satisfaction of current demands.In this study,flame-retardant rubber seed oil-based plasticize(FRP)was prepared via epoxidation reaction and ring opening addition reactions,which was used as a flame-resistant plasticizer for polyvinyl chloride to replace petroleum-based phthalate plasticizer.When DOP was replaced with FRP,the torque of PVC blends increased from 11.4 to 18.4 N⋅m,the LOI value increased from 24.3%for PVC-FRP-0%to 33.1%for PVC-FRP-20.The THR value diminished from 39 MJ/m^(2)(pertaining to PVC-FRC-0)to 22 MJ/m^(2)Tg increased from 23°C to 47°C,the weight loss of plasticized PVC blends significantly reduced from 22.6%to 2.8%in leaching tests.The study provided a new way to prepare flame retardant plasticizer using rubber seed oil as raw material.

Compressive Performance of Fiber Reinforced Recycled Aggregate Concrete by Basalt Fiber Reinforced Polymer-Polyvinyl Chloride Composite Jackets

The development of recycled aggregate concrete(RAC)provides a new approach to limiting the waste of natural resources.In the present study,the mechanical properties and deformability of RACs were improved by adding basalt fibers(BFs)and using external restraints,such as a fiber-reinforced polymer(FRP)jacket or a PVC pipe.Samples were tested under axial compression.The results showed that RAC(50%replacement of aggregate)containing 0.2%BFs had the best mechanical properties.Using either BFs or PVC reinforcement had a slight effect on the loadbearing capacity and mode of failure.With different levels of BFs,the compressive strengths of the specimens reinforced with 1-layer and 3-layer basalt fiber reinforced polymer(BFRP)increased by 6.7%–10.5%and 16.5%–23.7%,respectively,and the ultimate strains increased by 48.5%–80.7%and 97.1%–141.1%,respectively.The peak stress of the 3-layer BFRP-PVC increased by 42.2%,and the ultimate strain improved by 131.3%,relative to the control.This reinforcement combined the high tensile strength of BFRP,which improved the post-peak behavior,and PVC,which enhanced the structural durability.In addition,to investigate the influence of the various constraints on compressive behavior,the stress-strain response was analyzed.Based on the analysis of experimental results,a peak stress-strain model and an amended ultimate stress-strain model were proposed.The models were verified as well;the result showed that the predictions from calculations are generally consistent with the experimental data(error within 10%).The results of this study provide a theoretical basis and reference for future applications of fiber-reinforced recycled concrete.

油酸锌/脲嘧啶复合热稳定剂对PVC性能的影响

为了改善软质聚氯乙烯(PVC)的初始白度和长期热稳定性,制备由具有不饱和链的油酸锌和含氨基的脲嘧啶(6-氨基-1,3-二甲基脲嘧啶,DAU)组成的复合热稳定剂,添加合适的辅助稳定剂和增塑剂,进行聚氯乙烯热加工。采用刚果红试验法和干燥箱热老化试验法分析复合稳定剂对PVC静态热稳定性的影响;采用转矩流变测试评价其对PVC动态热稳定性的影响;利用红外光谱法研究复合稳定剂的热稳定机理。结果表明,油酸锌与脲嘧啶复合后,稳定剂与PVC的相容性提高,初始白度得到改善;复合稳定剂中DAU与油酸锌(DAU/Zn)的最佳比例为4∶1,长期热稳定性可达100 min;另外,加入辅助稳定剂和增塑剂使PVC的热稳定效果得到进一步改善。

纺膜参数对PVC中空纤维膜结构与性能的影响

以聚氯乙烯(PVC)和醋酸纤维素(CA)为膜材料,采用非溶剂致相分离(NIPS)法,通过改变纺膜参数制备了PVC中空纤维膜.结果表明:所制得的中空纤维膜具有致密皮层,断面为海绵孔与指状孔共存结构,纯水通量可达314 L/(m^(2)·h),BSA截留率可达95.0%,断裂强度22 MPa.此外,细中空纤维膜可在0.6 MPa压力以下稳定运行,并可对自来水中的有机物深度脱除49.30%.

裂纹-孔洞缺陷下PVC涂层织物类膜材的撕裂行为

膜结构节点和边界处往往需要通过膜面开孔来实现关键部位的连接,孔洞边缘的应力集中会影响膜面的撕裂行为。为探究聚氯乙烯(polyvinyl chloride,PVC)涂层织物类膜材中孔洞对裂纹扩展行为的影响,开展了含有裂纹-孔洞缺陷的PVC涂层织物类膜材的单轴拉伸试验,分析了裂纹扩展全过程和撕裂机理,提出了适用于含裂纹-孔洞多缺陷PVC涂层织物类膜材撕裂强度的预测模型,并验证了模型的适用性。研究结果表明:含裂纹-孔洞缺陷的PVC涂层织物类膜材在中心撕裂过程中存在裂纹端扩展和孔端再扩展两阶段;定义了裂纹端临界撕裂荷载、裂纹端峰值撕裂荷载、孔端临界撕裂荷载和孔端峰值撕裂荷载4项撕裂特征指标,以衡量含裂纹-孔洞缺陷膜材的抗撕裂性能;孔洞的存在导致试样在孔端再扩展阶段的承载力提升,但随着孔洞尺寸增大,孔端的承载力提升效应减弱,裂纹端峰值撕裂荷载逐渐变为控制试样破坏的极限荷载;所提出的二次函数-指数函数应力场模型能有效地预测膜材的裂纹端临界撕裂应力和孔端临界撕裂应力。

The Influence of Additives on Crystallization of Polyvinyl Chloride

Acetanilide, adipic acid and potassium hydrogen phthalate were chosen as nucleating agents of polyvinyl chloride（PVC）, and their effects on PVC crystallization were studied by differential scanning calorimetry, wide angle X-ray diffraction and fourier transform infrared spectroscopy. The experimental results indicate that all of the three additives are compatible with PVC to some extent, but adipic acid＇s compatibility with PVC is less satisfactory. The three additives can improve PVC crystallinity, and acetanilide can decrease PVC glass transition temperature（T）and narrow PVC melting range, while adipic acid and potassium hydrogen phthalate rise T of PVC and widen its melting range. All additives do not affect PVC crystal system and all g samples are in orthorhombic system. All additives can improve （200）, （110）, （210） and （201, 111） planes growing. Moreover, acetanilide and adipic acid can shrink PVC spacings and improve the crystal perfection of PVC, but potassium hydrogen phthalate swells spacings and reduces the perfection of PVC crystal.

2-氨基烟酸镧铈对PVC热稳定性的影响

以2-氨基烟酸(2-ANA)、Ce(NO_(3))_(3)、La(NO_(3))_(3)和NaOH为原料,合成出2-氨基烟酸镧铈(2-LCANA),研究2-LCANA及其复配稳定剂对聚氯乙烯(PVC)热稳定性能、流变性能和力学性能的影响。结果表明,2-LCANA及其复配稳定剂提高了PVC的热稳定性能,当m(2-LCANA)∶m(ZnSt_(2))∶m(PE)=2∶1∶2时,其热稳定时间为38 min,可以减小在加工过程中的损耗,增强PVC的力学性能,但是随着温度升高2-LCANA要比m(2-LCANA)∶m(ZnSt_(2))∶m(PE)=2∶1∶2的复配稳定剂抑制PVC降解反应发生更有效。2-LCANA能够吸收PVC降解释放的HCl气体,生成LaCl_(3)和CeCl_(3),减弱了HCl对PVC降解的催化作用,可以有效地阻止PVC链上C-Cl和与氯相连的C-H断裂,减少共轭双键的生成,减缓PVC变色,延缓了PVC的热降解。

Surface Sulfonation of Polyvinyl Chloride by Plasma for Antithrombogenicity

To enhance the blood compatibility of Polyvinyl Chloride (PVC) film, the film was modified by SO2/O2 gas plasma treatment. The effect of surface sulfonation of PVC treated by various SO2/O2 gas plasma depended on the volume ratio O2/(SO2 +O2). When the volume ratio was 0.5, the effect of sulfonation was the best. Sulfonic acid groups were specifically and efficiently introduced onto the PVC surface, which was proved by X-ray photoelectron spectroscopy (XPS) and Attenuated Total Reflectance Fourier Transfer Infrared (ATR-FTIR) spectroscopy. The surface microstructure of modified PVC film was studied with scanning electron microscopy (SEM). The antithrombogenicity of the samples was determined by the activated partial thromboplastin time (APTT), prothrombin time (PT), thrombin time (TT) and plasma recalcification time (PRT) tests and platelet adhesion experiment. The results indicated that the antithrombogenicity of modified PVC was improved remarkably.

Mo-MOF对软质PVC材料的阻燃及抑烟性能

采用熔融共混的方法将含钼离子的有机框架材料(Mo-MOF)添加到软质聚氯乙烯(PVC)材料中,利用极限氧指数(LOI)测试仪、NBS烟箱、锥形量热仪、拉伸强度测试仪等研究了材料的阻燃、抑烟及力学性能。测试结果表明,与软质PVC相比,当Mo-MOF的添加量为3%时,材料的LOI值由26.8%提高至30.3%,最大烟密度由918.5降低至471.2,总烟释放量(TSP)由25.23 m^(2)降低至12.02 m^(2),分别降低了48.7%及52.3%。此外,与PVC/MoO_(3)对比可知,当钼离子含量相同时,PVC/3%Mo-MOF材料的最大烟密度由774.0降低至471.2,TSP值由17.55 m^(2)降低至12.02 m^(2),分别降低了39.1%与31.5%。与MoO_(3)相比,Mo-MOF在PVC中的相容性及分散性更佳,在燃烧过程中形成了具有高比表面积的纳米级氧化钼,对PVC材料的阻燃及抑烟性能更佳。同时,随着Mo-MOF含量的增加,PVC材料的拉伸强度和断裂伸长率均得到了一定程度的提高。

加工型ACR的合成及在PVC中的应用

针对聚氯乙烯(PVC)/CaCO_(3)在混炼过程中存在的塑化困难、共混时间较长、不完全塑化等加工难点以及制品表面粗糙、无光泽等市场痛点,以叔十二烷基硫醇(TDDM)为链转移剂,设计并合成了一种加工型丙烯酸酯类共聚物(ACR-P)。探究了TDDM和ACR-P的添加量对PVC/CaCO_(3)/ACR-P复合材料力学性能、流变性能、微观形貌及塑化效果的影响。结果表明,随着TDDM添加量的增加,ACR-P特性黏度逐渐下降,PVC/CaCO_(3)/ACR-P复合材料的拉伸强度和储能模量明显提高,塑化时间大幅缩短,同时冲击强度略有增加。当TDDM添加质量分数为0.8%时,PVC/CaCO_(3)/ACR-P复合材料的拉伸强度达到52.79 MPa,与PVC/CaCO_(3)相比,提高了50.27%;塑化时间由71 s缩至32 s。ACR-P添加量的增加显著地影响了PVC/CaCO_(3)/ACR-P复合材料的力学性能和加工性能,当ACR-P添加量为10份时,复合材料的拉伸强度达到61.12 MPa,与PVC/CaCO_(3)相比,提高了87.6%;塑化时间由115 s缩至25 s。动态热机械分析测试显示PVC/ACR-P复合材料只有一个玻璃化转变峰,说明PVC树脂和ACR-P两相是一个相容体系。从扫描电子显微镜可以观察到PVC/CaCO_(3)复合材料中两相界面清晰,ACR-P的引入使复合材料的界面变得模糊,这表明复合材料的相容性得到改善,力学性能和加工性能得到提升。

Thermogravimetric characteristics and different kinetic models for medical waste composition containing polyvinyl chloride-transfusion tube

Thermogravimetric study of medical transfusion tube(MTT) waste containing polyvinyl chloride(PVC) was carried out using the thermogravimetric analyser(TGA) with N2, at different heating rates of 5, 10, 20, 30, 50 °C/min. The purpose is to obtain pyrolysis characteristics and kinetic parameters of medical waste. The experimental results indicate that the pyrolysis behavior of the MTT sample is in agreement with its main ingredient of PVC, appearing two stair stepping stages. The influence of the additives in MTT on pyrolysis behavior was also revealed, which could improve MTT pyrolysis at lower temperature in the first stage, and cause obvious unsmoothness and asymmetry of the second DTG peak. Four n-order kinetic models of Coats-Redfern, Ozawa, Kissinger and Freeman-carroll were used to get the kinetic parameters. Furthermore, a novel "two-step four-reaction model" was established to simulate the whole continuous process. The different methods and the kinetic parameters thus obtained were discussed and compared with each other in literatures. The reasons of deviation among kinetic values were tried to be elucidated. The new established model could more satisfactorily describe the pyrolysis process of MTT, being more mechanistic and conveniently serving for the engineering.

两种镁盐复配在改性PVC能源线缆中的应用

两种镁基无机矿物粉体是绿色环保的天然产物,分别可以在热稳定性和抑烟性能方面实现更宽区间、更大范围优势互补,采用物理研磨法分别制备了水镁石粉(MH)和不同目数的水菱镁石粉(HM),并尝试将MH复配不同目数的HM粉体添加到聚氯乙烯(PVC)能源电线电缆中制备复合材料。利用极限氧指数、烟密度测试箱、万能力学实验机和热失重仪等对该PVC能源电线电缆的燃烧性能、烟密度、力学性能和热性能等进行了测试,并且使用拉曼光谱仪、扫描电子显微镜和能谱仪对最终的燃烧残炭进行了检测。结果表明,MH复配高目数HM能够在一定程度上提高PVC复合材料的阻燃特性,尤其是最大烟密度和烟密度等级分别下降了33.6%和42.9%;同时,可以有效地提高PVC能源电线电缆的热稳定性,体现在初始降解温度和热解50%时温度分别提高了5.3%和56.5%,且能够大幅提高燃烧后的残炭率,在600℃和800℃分别提升了3.6倍和4.3倍。MH和高目数HM复配添加还能够有效改善残炭的有序化程度,使得残炭更为致密连续,既能够有效地抵抗热流、质流和气流的传递,又能促进MgO在残炭表面的凝聚,有效提升物理阻隔效果。最后,物理法制备高目数镁基粉体价格低廉,综合应用成本低。

玻璃粉对陶瓷化PVC复合材料性能影响

探讨了玻璃粉用量对陶瓷化聚氯乙烯(PVC)复合材料性能的影响。结果表明,添加60份自制玻璃粉,PVC复合材料综合性能较好,材料硬度(邵氏D)可达41,氧指数达到30%。随着玻璃粉含量增大,复合材料内部孔洞变多自支撑力改变,在600℃烧蚀30 min后所形成的陶瓷体成瓷效果好,结构密实且强度高、自支撑能力强、内部孔洞少、瓷化作用明显。

Preparation and Properties of Polyvinyl Chloride/Carbon Nanotubes Composite

Chemically functionalized carbon nanotubes were combined with PVC to enhance both toughness and strength by simply mixing long alkyl chain modified multi-wall carbon nanotubes (abbreviated as MWNTs) or Ester-functionalized soluble MWNTs (abbreviated as eMWNTs) with PVC in Tetrahydrofuran (THF)/Cyclohexanone (CH) solution to obtain good dispersity solution. The MWNTs modified with 1-Bromohexadecane can effectively increase the intermolecular force with PVC by hydrogen bond. The obtained nanocomposite has a regular shape with homogeneously dispersed particles. PVC/2 wt% eMWNTs has been proved to possess excellent thermal stability. The intermolecular force between eMWNTs and PVC endows the as-fabricated nanocomposite with enhanced toughness and strength, indicating that our method is promising for wide use in PVC/eMWNTs nanocomposition.

Synthesis and Characterization of Phenyl Camellia oleifera Seed Oil Ester Plasticizing PVC

Plasticizers are essential additives in the processing of polyvinyl chloride(PVC),with phthalate plasticizers being widely used.However,these conventional plasticizers have been shown to be harmful to human health and environmentally unfriendly,necessitating the exploration of eco-friendly bio-based alternatives.In this study,Camellia oleifera seed oil,a specialty resource in China,was utilized as a raw material and reacted with 4,4′-Methylenebis(N,N-diglycidylaniline)(AG-80)to synthesize Phenyl Camellia seed Oil Ester(PCSOE).PCSOE was employed as a plasticizer to prepare modified PVC films with varying concentrations,with the conventional plasticizer dioctyl phthalate(DOP)serving as a control.Experimental results demonstrate that PSCOE-plasticized PVC films exhibit enhanced hydrophilicity,tensile strength,and thermal stability compared to DOP-modified PVC films.The contact angle of PSCOE-plasticized PVC films ranges from 66.26°to 78.48°,which is generally lower than the contact angle of DOP-modified PVC films at 78.40°,indicating improved hydrophilicity due to the modification with PCSOE.The tensile strength of PSCOE-plasticized PVC films ranges from 17.73 to 20.17 MPa,all surpassing the value of 16.41 MPa for DOP-modified PVC films.Moreover,the temperatures corresponding to 5%,10%,and 50%weight loss for PVC samples modified with PCSOE are higher than those for DOP.Hence,PCSOE presents a viable alternative to DOP as a plasticizer for PVC materials.

PVC树脂产品质量提升总结

针对PVC树脂“鱼眼”数超标问题,进行了系统排查分析。通过采取增大注水速率,调整助剂配方和用量等措施,减少了PVC树脂中的“鱼眼”,提高了产品的优等品率。

SYNERGISTIC MODIFICATION OF EPDM AND CROSSLINKING AGENT IN IMMISCIBLE BLENDS OF POLYVINYL CHLORIDE WITH LOW DENSITY POLYETHYLENE

The synergism of ethylene-propylene-diene monomer copolymer （EPDM） and dicumyl peroxide （DCP, a crosslinking agent） in low density polyethylene （LDPE）/poly（vinyl chloride） （PVC） blends was investigated. When EDPM and DCP are added to the blends simultaneously, the tensile properties could be improved significantly, especially for the blends with LDPE matrix. For example, incorporation of 10/1 （mass ratio） EPDM/DCP improves the tensile strength of the LDPE/PVC （mass ratio 80/20） blend from 7.9 MPa to 8.5 MPa and the elongation at break from 25% to 503%. Results from selective extraction, phase-contrast microscopy and thermal analysis reveal that the improvement in the tensile properties of the blends with LDPE matrix is principally due to the formation of a fine crosslinking network of the LDPE and EPDM phase. The outstanding modification effect of EPDM is explained by its dual functions： molecular entanglement with LDPE and the enhanced efficiency of DCP in the blends.

Molecular Dynamics Simulation Studies on the Cooling Process of Polyvinyl Chloride

By means of molecular dynamics simulation, the transition of the conformations of polyvinyl chloride during a cooling process from 600 to 300 K was studied. The results show that the amorphous polyvinyl chloride chain experiences the melting state, elastic state and glass state and the conformations can be characterized by the increases of the trans-state of C--C--C--C and the near gauche-state of C--C--C--C1 with the decrease of temperature. It is found that the transition of the conformations is driven mainly by the Coulomb interaction between chain segments.

STUDY ON THE MORPHOLOGY OF POLYVINYL CHLORIDE/POLYSTYRENE BLENDS BY ELECTRON MICROPROBE ANALYSIS

The morphology of polyvinyl chloride/polystyrene (PVC/PS) blend samples with different mass ratios, prepared by means of solution casting and melt mixing, have been successfully examined by electron microprobe analysis (EMP). This experiment was performed in a scanning electron microscope attached to an energy dispersive X-ray analyzer. Differential scanning calorimetry was also used to investigate the phase separation of the blends. The results show that PVC and PS are incompatible and the blends have sea-islands phase structures. Blends prepared via melt mixing have finer phase-dispersion than those prepared via solution casting.

氯化石蜡/DOTP复合增塑体系在PVC中的应用

为得到低成本的PVC增塑剂配方,对氯化石蜡(CP-52)和对苯二甲酸二辛酯(DOTP)在聚氯乙烯(PVC)中的协同增塑性能进行研究,对比氯化石蜡复配前后,PVC制片的性能变化,包括热稳定性能、耐热老化性能、力学性能和增塑剂的耐迁移性能。结果表明,由于氯化石蜡具有耐挥发和阻燃性较好的特点,CP-52/DOTP复合增塑体系增塑的PVC制片具有较好的热稳定性能,其耐热老化性能和耐挥发性能均提高。另外,复配氯化石蜡后,可以显著提高PVC制片的力学性能,当复配比例为40%时,断裂伸长率和拉伸强度提高最显著,分别为0-CP-52/DOTP试片的1.92倍和2.28倍。复配氯化石蜡后,对PVC制片的耐迁移性能也有提高,在无水乙醇和石油醚中,当复配比例为50%时,PVC制片的质量损失率分别降低了6.87%和17.16%(6 h)。在食品模拟液中的耐迁移性能也得到提升,在正己烷中,当复配比例为50%时,PVC制片的质量损失率降低了14.97%。最后,对CP-52/DOTP复合增塑体系提出对应的增塑机理。